FR2799120A1 - Material comprising UV-A organic solar filter, used in cosmetic and dermatological compositions, contains zirconium alkoxide, organic or silicone functionalized polymer and solvent - Google Patents

Abstract

The material comprises: (a) at least one zirconium alkoxide, (b) at least one UV-A organic solar filter with maximum absorption wavelength below 370 nm, (c) at least one functionalized organic polymer or its precursor, or functionalized silicone polymer or its precursor, d) at least one solvent, and (d) sufficient water quantity for partial and/or total hydrolysis of zirconium alkoxide and its condensation. The material has maximum absorption wavelength 370-400 nm. Independent claims are also included for: (i) a process of moving maximum absorption wavelength ( lambda max) of UV-A organic solar filter from its original level below 370 nm to the spectrum range 370-400 nm, comprising associating the filter with the sol material (comprising components (a), (b), (c), (d) and (e) as described) as claimed, with zirconium alkoxide (a) preferably mixed with solution of polymer (c) before the addition of solar filter (b); and (ii) a cosmetic and/or dermatological composition comprising 1-99 (preferably 5-60) wt.% of material as claimed, optionally in form of particles obtained by drying and grinding, of particle size 0.1-20 (preferably 0.1-10) nm, and optional additive selected from other organic solar filters, bronzing and/or artificial tanning agents, pigments, fats, organic solvents, thickeners and antioxidants.

Description

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MATERIAL COMPRISING AN ORGANIC UV-A FILTER
AND METHOD FOR MOVING LENGTH
MAXIMUM ABSORPTION WAVE
The present invention relates generally to a material obtained by the sol-gel route having a maximum absorption wavelength (#max) in the range from 370 to 400 nm, a method for shifting the wavelength d maximum absorption of a material comprising an organic UV-A sunscreen, as well as a cosmetic and / or dermatological composition including such a material.

 We know that light radiation of wavelengths between 280 nm and 400 nm allows the browning of the human epidermis and that rays of wavelengths between 280 nm and 320 nm, known under the name of UV -B, cause erythema and skin burns which can affect the development of natural tanning; this UV-B radiation must therefore be filtered.

 We also know that UV-A rays, with wavelengths between 320 and 400 nm, which cause browning of the skin, are capable of inducing an alteration of the latter, in particular in the case of skin. sensitive or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity in the skin and the appearance of wrinkles, leading to premature aging. They promote the initiation of the erythematous reaction or amplify this reaction in certain subjects and can even be at the origin of phototoxic or photoallergic reactions. It is therefore desirable to also filter UV-A radiation.

 Among the commonly used sun filters, there are no effective organic filters in the long UV-A spectral range corresponding to wavelengths from 370 to 400 nm. In other words,

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 sun protection is not ensured in this spectral range. This is all the more serious since this more penetrating radiation is partly responsible for the development of certain skin cancers and immunosupression as well as skin photoaging.

 In the prior art, PCT patent applications numbers WO 93/10753 and WO 93/11135 of Slavtcheff et al disclose respectively a metal complex type solar filter of dibenzoylmethane derivatives, the wavelength of which maximum absorption is equal to 366 nm, and a process for the preparation of this new solar filter. At present, there are no known suitable organic UV-A sun filters having a maximum absorption wavelength (#max) greater than or equal to 370 nm with an extinction coefficient #> 30,000 mol- 1cm-1.

 It was surprisingly found that by combining an organic UV-A filter having a maximum absorption wavelength (#max) less than 370 nm, such as 4-tert-butyl-4'-methoxydibenzoylmethane ( Parsol # 1789 - #max = 358 nm), with certain zirconium compounds, it is possible to obtain a material whose absorption band is displaced and which has a maximum absorption wavelength in the interval going from 370 to 400 nm, with an at least comparable value of #.

 The present invention therefore relates to a material capable of being obtained by sol-gel route, comprising at least one organic UV-A solar filter of, max less than 370 nm and at least one zirconium compound, the material having a length wave of maximum absorption which lies in the range from 370 to 400 nm.

 The present invention also relates to a method for moving the maximum absorption wavelength of an organic UV-A solar filter of #max less than 370 nm, in the range from 370 to 400 nm.

 The present invention also relates to cosmetic and / or dermatological compositions for the photoprotection of the skin and / or keratin materials, comprising a material of the invention.

 Other characteristics, aspects and advantages of the invention will appear more clearly on reading the description and the examples which follow.

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 An object of the present invention is a material capable of being obtained by the sol-gel route which has a maximum absorption wavelength (#max) in the range from 370 to 400 nm and which comprises: (a ) at least one zirconium alkoxide, (b) at least one organic UV-A solar filter whose maximum absorption wavelength is less than 370 nm, (c) at least one functionalized organic polymer or a precursor of such a polymer, or at least one functionalized silicone polymer or a precursor of such a polymer, (d) at least one solvent, and (e) an amount of water sufficient for the partial and / or total hydrolysis of the zirconium alkoxide and its condensation.

 The term organic UV-A sunscreen means any organic compound absorbing UV radiation in the wavelength range 320-400 nm.

The zirconium alkoxide is chosen from the group consisting of: (1) the alkyl zirconates corresponding to one of the following formulas: Zr (ORI) 4 (la) R-Zr (ORl) 3 (Ib) ( R1O) 3Zr-R "-Zr (OR1) 3 (le) R-Zr (ORI) 2 (Id)
R 'in which: RI represents a linear or branched alkyl group, in CI-30, preferably in CI-6, R and R', independently of each other, represent a linear or branched alkyl group, a group cycloalkyl, a substituted or unsubstituted aryl group, said groups R and R ′ being able to be substituted by groups capable of reacting with the functionalized organic or silicone polymer such as, for example, ethylenically unsaturated groups such as (meth) acrylic groups and vinyl, halogenated, hydroxylated, carboxylated, thiols, epoxy, esters, phosphonic groups, phosphates, phosphonates, ureido, urethanes, amines, amides, amino acids and polypeptides, acetic acid, acetoacetate (ACAC), ethylaceous-

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toacetate, or a group deriving from EDTA and its derivatives, etc., and said groups R and R ′ which can additionally comprise a cosmetically or dermatologically active group chosen, for example, from a coloring group, a photochromic group, a filtering group UV radiation, a group promoting adhesion to keratin materials (such as groups of amide, urethane, urea, hydroxy, carboxy, amino acid or polypeptide), a group facilitating make-up removal, a bactericidal group, a chelating group which can in particular complexing multivalent cations, a hydroxy acid, a neurosuppressant, an anti-hair loss group, an antioxidant group, an anti-free radical group or a vitamin-carrying group, R "represents a linear or branched alkylene group, a cycloalkylene group, a substituted or unsubstituted arylene group, said group R "possibly being substituted by groups capable of reacting with the organic or silicone polymer such as those defined above, and which may additionally comprise a cosmetically or dermatologically active group such as those defined above; (2) alkyl zirconate complexes corresponding to one of the following formulas:
Zr (OR1) 4-x (X) x (IIa)
R-Zr (OR1) 3-x (X) x (IIb) (X) x (ORI) 3-x Zr-R "-Zr (ORI) 3-x (X) x (Ile)
R-Zr (OR1) 2-x (X) x (IId)
R 'in which: X represents a monodentate ligand comprising a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom, which can be covalently linked to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer (c) such as, for example, ethylenically unsaturated groups such as (meth) acrylic and vinyl groups, halogenated, hydroxylated, carboxylated groups, thiols, epoxy, esters, phosphonic groups, phosphates, phosphonates, ureido, urethanes, amines, amides, amino acids and polypeptides, the acetic acid group, acetoacetate (ACAC), ethylacetoacetate, or a group deriving from EDTA and its derivatives, and being able to include

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 a cosmetically or dermatologically active group as those defined above, x represents the number of chelating groups X, R, R ', R "and RI have the same meanings as those given for the formulas (la) to (Id) below above; (3) chelated alkyl zirconates corresponding to the following formula: Zr (ORI) 4-bx '(X') x '(III) in which: RI has the same meaning as for formulas (la) to (Id) above, b represents the number of binding atoms of the chelating group X ', x' represents the number of chelating groups X ', X' represents a chelating group or polydentate ligand comprising a nitrogen atom, an atom of phosphorus, a sulfur atom and / or an oxygen atom, which can be covalently linked to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer (c), as defined above, and which can have a cosmetically or dermatologically active group such as those defined above s.

 By monodentate ligand (X) is meant a group comprising a single atom capable of bonding with the central metallic atom. As examples of such ligands, mention may be made of carboxylic acids and ketones.

thyle, l'e-N-méthacryloyl-L-lysine, l'acide méthacrylamino-4- ou -5-sa- licylique. By chelating group (X ′) is meant a polydentate ligand linked to a single central metal atom by more than one doublet donor atom. It is preferably chosen from [3-diketones, ss-ketoesters, ss-ketoamines, [alpha] - and P-hydroxy acids, optionally sshydroxylated amino acids, salicylic acid and its derivatives. Mention may in particular be made of acetoacetoxyethyl methacrylate, a-hydroxymethacrylate of

thyle, e-N-methacryloyl-L-lysine, methacrylamino-4- or -5-salicylic acid.

 Among the zirconium alkoxides mentioned above, very particularly preferred are tetra-n-propyl zirconate and tetra-isopropyl zirconate.

 The organic UV-A sunscreen having a #max less than 370 nm can be any suitable organic compound having a maximum absorption wavelength less than 370 nm.

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dans laquelle :
R7 et R9, identiques ou différents, représentent un atome d'hydrogène, un atome d'halogène, un groupe OH, un groupe alkyle saturé ou non, linéaire ou ramifié en CI-CI(), un groupe alcoxy saturé ou non, linéaire ou ramifié en Ci-CI(), ou un groupe HS03 ;
R10 représente un atome d'hydrogène ou HS03 ; Rg représente un groupe hydroxy ; groupe OR11 où R11 repré- sente un groupe alkyle, saturé ou insaturé, linéaire ou ramifié en C1-C10 ; ou bien un groupe de structure suivante :

dans laquelle R12 représente un atome d'hydrogène ou HS03 ; ou bien un groupe de formule suivante :

ou bien un un groupe de formule suivante :

Among the organic UV-A sunscreens which can be used according to the invention, mention may be made of: (1) dibenzoylmethane derivatives; (2) the active filters in the UV-A of formula (IV) below:

in which :
R7 and R9, identical or different, represent a hydrogen atom, a halogen atom, an OH group, a saturated or unsaturated, linear or branched C1-CI alkyl group (), a saturated or unsaturated alkoxy group, linear or branched in Ci-CI (), or a group HS03;
R10 represents a hydrogen atom or HS03; Rg represents a hydroxy group; group OR11 where R11 represents an alkyl group, saturated or unsaturated, linear or branched in C1-C10; or a group with the following structure:

in which R12 represents a hydrogen atom or HS03; or a group of the following formula:

or a group of the following formula:

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dans laquelle :
W représente un atome d'oxygène ou un groupe-NH- ;
R17 représente un atome d'hydrogène ou HS03 ;
R18 représente un groupe alcoxy, linéaire ou ramifié, comportant de 1 à 10 atomes de carbone environ ou un groupe de formule suivante :

dans laquelle Y représente un atome d'oxygène ou un groupe-NH- ;
R19 représente un atome d'hydrogène ou HS03 ; (4) les dérivés de benzophénone tels que ceux de formule (VI) suivante :

in which :
Z represents an oxygen atom or an NH- group;
R13, R14, R15 and R16, identical or different, represent a hydrogen atom, a halogen atom, an OH group, an alkyl group, saturated or unsaturated, linear or branched C1-C10; a linear or branched C1-C10 alkoxy group, saturated or not; or an HS03 group; (3) active filters in UV-A of the benzimidazole or benzoxazole type of formula (V) below:

in which :
W represents an oxygen atom or an NH- group;
R17 represents a hydrogen atom or HS03;
R18 represents an alkoxy group, linear or branched, comprising from 1 to 10 carbon atoms approximately or a group of the following formula:

in which Y represents an oxygen atom or a group -NH-;
R19 represents a hydrogen atom or HS03; (4) benzophenone derivatives such as those of formula (VI) below:

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in which :
R20 represents a hydrogen atom or an alkyl group, saturated or not, linear or branched C1-C10; R21 and R22, identical or different, represent a hydrogen atom, a halogen atom, an OH group, an alkyl group, saturated or unsaturated, linear or branched in Ci-CI (); an alkoxy group, saturated or not, linear or branched in C1-C10 or an HS03 group; R23 represents a hydrogen atom, OH, an alkyl group, saturated or not, linear or branched in C1-C10 or an alkoxy group, saturated or not, linear or branched in C1-C10; R24 represents OH, a hydrogen atom or an alkyl group, saturated or not, linear or branched in C1-C10; (5) silane derivatives or polyorganosiloxanes with group (s) none such as those described in documents EP-A-0 389 377, FR-A- 2 657 351 and EP-A-0 655 453; (6) anthranilates; (7) their mixtures.

 Among the dibenzoylmethane derivatives which are particularly suitable in the context of the present invention, there may be mentioned, without limitation, 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, , 4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-methyl-5-isopropyl '-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.

 Among the dibenzoylmethane derivatives mentioned above, particularly preferred is 4-tert-butyl-4'-methoxydibenzoylmethane,

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sold in particular under the trade name of "PARSOL 1789" by the company HOFFMANN-LAROCHE, this filter corresponding to the following developed formula:

Another preferred dibenzoylmethane derivative according to the present invention is 4-isopropyldibenzoylmethane, sold under the name of "EUSOLEX 8020" by the company MERCK, and corresponding to the following structural formula:

The compounds of structures (IV) above are described respectively in US Pat. No. 4,585,597 and patent applications FR 2,236,515, 2,282,426.2 645 148.2 430,938 and 2,592,380.

benzène- l,4-[di(3-méthylidènecampho-10-sulfonique)] tel que le pro- duit vendu sous le nom MEXORYL SX par la société CHIMEX. A particularly preferred compound of formula (IV) is the acid

benzene-1,4- [di (3-methylidenecampho-10-sulfonic)] such as the product sold under the name MEXORYL SX by the company CHIMEX.

 Benzene-1,4- [di (3-methylidenecamphosulfonic acid)] and its various salts (compound D), described in particular in patent applications FR-A-2 528 420 and FR-A-2 639,347, are filters already known per se (so-called broadband filters) capable of absorbing ultraviolet rays of wavelength ranging from 280 nm to 400 nm, with absorption maxima of between 320 and 370 nm, especially around 345 nm. These filters have the following general formula:

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dans laquelle D représente un atome d'hydrogène, un métal alcalin ou encore un groupe NH(R25)3+ dans lequel les groupes R25 qui peuvent être identiques ou différents, représentent un atome d'hydrogène, un groupe alkyle ou hydroxyalkyle en C1-C4 ou encore un groupe Mn+/n, Mn+ représentant un cation métallique polyvalent dans lequel n est égal à 2 ou 3 ou 4, Mn+ représentant de préférence un cation métallique choisi parmi Ca2+, Zn2+, Mg2+, Ba2+, Al3+ et Zr4+. Il est bien entendu que les composés de formule (IV) ci-dessus peuvent donner lieu à l'isomère "cis-trans" autour d'une ou plusieurs double (s) et que tous les isomères rentrent dans le cadre de la présente invention.

in which D represents a hydrogen atom, an alkali metal or even an NH (R25) 3+ group in which the R25 groups which may be identical or different, represent a hydrogen atom, a C1-6 alkyl or hydroxyalkyl group C4 or also a group Mn + / n, Mn + representing a polyvalent metal cation in which n is equal to 2 or 3 or 4, Mn + preferably representing a metal cation chosen from Ca2 +, Zn2 +, Mg2 +, Ba2 +, Al3 + and Zr4 +. It is understood that the compounds of formula (IV) above can give rise to the “cis-trans” isomer around one or more double (s) and that all the isomers fall within the scope of the present invention. .

- l'acide benzène-1,4-di(benzimidazol-2-yl-5-sulfonique), - l'acide benzène-l,4-di(benzoxazol-2-yl-5-sulfonique) ainsi que leurs formes partiellement ou totalement neutralisées. Mention may be made, as examples of specific benzimidazole or benzoxazole compounds, corresponding to formula (V):

- benzene-1,4-di acid (benzimidazol-2-yl-5-sulfonic), - benzene-1,4-di acid (benzoxazol-2-yl-5-sulfonic) as well as their partially forms or totally neutralized.

 Among the benzophenone derivatives of formula (VI), there may be mentioned more particularly those chosen from the group consisting of: - 2,4-dihydroxybenzophenone (benzophenone-1), such as the product sold under the name UVINUL 400 by BASF; - 2,2 ', 4,4'-tetrahydroxybenzophenone (benzophenone-2), such as the product sold under the name UVINUL D50 by BASF; - 2-hydroxy-4-methoxybenzophenone also called oxybenzone (benzophenone-3), like the product sold under the name UVINUL # M40 by BASF; - 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, also called sulisobenzone (benzophenone-4), as the product sold under the name UVINUL # MS40 by BASF; as well as its sodium sulfonate form (benzophenone-5);

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 - 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (benzophenone-6), such as the product sold under the name HELISORB 11 by NORQUAY; - 5-chloro-2-hydroxybenzophenone (benzophenone-7); - 2,2'-dihydroxy-4-methoxybenzophenone, also called dioxybenzone or benzophenone-8, as the product sold under the name SPECTRASORB UV-24 by AMERICAN CYANAMID; - the disodium salt of the 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid or benzophenone-9 diacid, such as the product sold under the name UVINUL DS49 by BASF; - 2-hydroxy-4-methoxy-4'-methylbenzophenone (benzophenone-10); - Benzophenone-11 as the product sold under the name UVINUL M493 by BASF; - 2-hydroxy-4- (octyloxy) benzophenone (benzophenone-12).

 Among the anthranilates which can be used according to the present invention, mention may very particularly be made of menthyl anthranilate such as the product sold under the name NEO HELIOPAN MA # by the company Haarman & Reimer.

 The functionalized organic or silicone polymer of the material according to the invention may be a random, block and / or grafted homopolymer or copolymer chosen from: (a) homopolymers and copolymers of alkyloxazoline such as poly (2-ethyl- 2-oxazoline); (b) homopolymers and copolymers of (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene-sulfonic acid, acrylamido-2-methylpropane-sulfonic acid, methacrylate 2-sulfoethyl, vinylsulfonic acid and / or vinylphosphonic acid; (c) homopolymers of acrylic or methacrylic esters or amides, and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, sty - rene, substituted styrenes such as hydroxystyrene, fluoro- and perfluoro-olefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds such as fluorinated vinyl ethers, and unsaturated organosiloxanes or organopolysiloxanes;

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 (d) homopolymers and copolymers of vinyl alcohol; (e) homopolymers of vinyl and / or allyl esters or amides and / or methallylics, and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulphonic acids, phosphonic acids, vinyl esters and ethers , olefins, styrene, substituted styrenes such as hydroxystyrene, fluoro- and perfluoro-olefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds such as fluorinated vinyl ethers, and organosilanes, organosiloxanes or unsaturated organopolysiloxanes; (f) polyethers such as homopolymers and copolymers of methylene oxide, ethylene oxide, propylene oxide or tetramethylene oxide; (g) aromatic and / or aliphatic polyesters and polyesters obtained by ring opening, such as polycaprolactones, poly-lactides, polyglycolides and their copolymers; (h) homopolymers and copolymers of olefins or of cyclo-olefins, such as polyethylenes, ethylene / vinyl acetate, ethylene / oc-olefin, ethylene / cyclo-olefin, ethylene / (meth) acry- late and homopolymers and copolymers of propylene, butene, isobutene and norbornene; (i) polyamides, polyesteramides and polyether amides; (j) polyurethanes and polyureas which may contain polyether, polyester and / or polyorganosiloxane blocks, optionally fluorinated; (k) fluoropolymers such as the products sold by the company Ausimont under the name of "Fomblin" (perfluoropolyether); (1) natural polymers and modified natural polymers such as ethers and / or esters of cellulose or starch, polysaccharides, glycosaminoglucans and oligosaccharides, natural gums such as hydroxyalkylated guar gums such as hydroxypropylated, hydroxypropylated guar gums with carboxylic or quaternized functions, locust bean gum, xanthan gum, carrageenans, pectins, alginates, polypeptides or proteins such as collagen , elastin, gelatin

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 or keratin; (m) polyorganosiloxanes such as polydimethylsiloxanes, poly-methylphenylsiloxanes, polyphenylsiloxanes, polyorganosiloxanes substituted on the chain or at the chain end with amino acid groups, polyoxyethylene chains, amino or polyamino groups, hydroxy groups , carboxylic acid groups, alkyl chains, vinyl or acrylic grafts or sequences, fluorinated or perfluorinated grafts or sequences; (n) polyorganophosphazenes; (o) polysilanes, polycarbosilanes or polysilazanes; and (p) mixtures of these polymers.

 In a particular embodiment, the hydrocarbon homopolymers and copolymers as mentioned above, can be sequenced and / or grafted by polysiloxane chains.

 The organic or silicone polymers can also contain a cosmetically or dermatologically active group such as those listed above.

 In the case where organic or silicone polymers are not functionalized, they can be either by reaction within the composition itself, such as, for example, in the case of polyorganosiloxanes, or by prior reaction by the usual methods before formation. of composition.

 Among the organic or silicone polymers preferred according to the invention, there may be mentioned in particular poly (2-ethyl-2-oxazoline), terpolymer of vinyl acetate, of vinyl 4-tert-butyl benzoate and of crotonic acid (65/25/10), polydimethylsiloxane-diols, polyethylene glycols, poly (vinyl alcohol and poly (vinyl pyrrolidone). Polydimethylsiloxane-diols are the most preferred.

 When the material according to the invention contains a precursor of the organic or silicone polymer, it is essentially one or more monomers capable of leading to an organic or silicone polymer functionalized by polymerization of unsaturated double bonds or by polycondensation during l application of the composition.

 The polymerization can be initiated conventionally thermally in the presence of conventional free radical initiators, by

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 irradiation with UV radiation, by electron beams by ionic means (cationic or anionic) or by any known technique of polymerization.

 Although this particular embodiment can be implemented according to the invention, it is nevertheless preferred, for practical reasons, to use an organic or silicone functionalized polymer already formed.

 The solvent used in the material of the present invention is preferably a lower, linear or branched alcohol, more preferably ethanol.

 The generally used amounts of the various components of the material are the following, expressed relative to the total weight of the material: - from 0.1% by weight to 99% by weight, preferably from 0.5% by weight to 80% by weight , and better still from 1% by weight to 70% by weight of zirconium alkoxide, from 0.1% by weight to 99% by weight, preferably from 0.5% by weight to 80% by weight, and more preferably from 1% by weight to 70% by weight of functionalized organic or silicone polymer, - from 0.1% by weight to 30% by weight, preferably from 0.1% by weight to 20% by weight, and better still from 0.1% by weight to 15% by weight of sunscreen.

 Another object of the present invention relates to a method for moving in the range from 370 to 400 nm, the maximum absorption wavelength (#max) of an organic UV-A filter having a #max less than 370 nm, which consists in combining with said filter a sol comprising at least one functionalized organic polymer or a precursor of this polymer, or at least one functionalized silicone polymer or a precursor of this polymer, at least one zirconium alkoxide, at least one solvent , and an amount of water sufficient for the partial and / or total hydrolysis of the zirconium alkoxide and its condensation. All components are as defined above.

 According to a preferred embodiment of the process of the invention, the zirconium alkoxide is mixed with a polymer solution before the addition of the filter.

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 A further object of the present invention is a cosmetic and / or dermatological composition, comprising, in a cosmetically and / or dermatologically acceptable carrier, a material according to the present invention, as defined above.

 This cosmetic and / or dermatological composition comprises the material according to the invention, in an effective amount ranging from 1% by weight to 99% by weight, preferably from 5% by weight to 60% by weight, relative to the total weight of the composition. Preferably, the material according to the invention is dried and ground and added in the form of particles in the composition. The average particle size obtained after drying and grinding is in the range from 0.1 m to 50 m, preferably from 0.1 m to 20 m, and more preferably from 0.1 m to 10 m.

 The cosmetic and / or dermatological compositions targeted by the present invention may of course contain one or more complementary, hydrophilic or lipophilic sun filters, different from the organic UV-A sun filters defined above. These additional filters can be chosen in particular from cinnamic acid derivatives, salicylic derivatives, camphor derivatives other than those corresponding to formula (IV), triazine derivatives such as those described in patent applications EP- A-863145, EP-A-517104, EP-A-57083 8, EP-A-796851, EP-A-775698 and EP-A-878469, ss derivatives, ssdiphenylacrylate, p- acid derivatives aminobenzoic acid, filter polymers and filter silicones described in application WO-93/04665.

 As examples of complementary active sunscreens, mention may be made of: - p-aminobenzoic acid, - ethoxylated p-aminobenzoate (25 moles), - 2-ethylhexyl p-dimethylaminobenzoate, - ethyl p-aminobenzoate N -proproxylated, - glycerol p-aminobenzoate, - homomenthyl salicylate, - 2-ethylhexyl salicylate, - triethanolamine salicylate, - 4-isopropylbenzyl salicylate, - 2-ethylhexyl 4-methoxycinnamate,

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l'-oxycarbonyl)anilino]-1,3,5-triazine, - la 2,4-bis {[4-(2-éthylhexyloxy)-2-hydroxy]-phényl}-6-(4- méthoxy-phényl)-1,3,5-triazine, - les polyorganosiloxanes à fonction benzalmalonate. - methyl diisopropylcinnamate, - isoamyl 4-methoxycinnamate, - diethanolamine 4-methoxycinnamate, - 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, - 2-cyano-3,3-diphenylacrylate ethyl, - 3- (4'-methylbenzylidene) -d, l-camphor, - 3-benzylidene-d, l-camphor, - 2,4,6-tris- [p- (2'- ethylhexyl-l'-oxycarbonyl) anilino] -1,3,5-triazine, la 2 - [(p- (tertiobutylamido) anilino] -4,6-bis - [(p- (2'-ethylhexyl-

1'-oxycarbonyl) anilino] -1,3,5-triazine, - 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxy-phenyl) -1,3,5-triazine, - polyorganosiloxanes with benzalmalonate function.

 The cosmetic and / or dermatological compositions according to the invention may also contain agents for tanning and / or artificial browning of the skin (self-tanning agents) such as, for example, dihydroxyacetone (DHA).

 The cosmetic and / or dermatological compositions according to the invention may also contain pigments or else nanopigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 and 50 nm) of coated metal oxides or no, for example, titanium oxide nanopigments (amorphous or crystallized in rutile form and / or anatase) of iron, zinc, zirconium or cerium which are all well-known photoprotective agents acting by physical blocking (reflection and / or diffusion) of UV radiation. Conventional coating agents are moreover alumina and / or aluminum stearate. Such nanopigments of metal oxides, coated or uncoated, are in particular described in patent applications EP-A-0 518 772 and EP-A-0 518 773.

 The cosmetic and / or dermatological compositions in accordance with the present invention may also comprise conventional cosmetic adjuvants, in particular chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-radical agents free, opacifiers,

<Desc / Clms Page number 17>

 stabilizers, emollients, silicones, α-hydroxy acids, defoamers, moisturizers, vitamins, fragrances, preservatives, surfactants, fillers, sequestrants, polymers, propellants, alkalizing agents or acidifiers, dyes or any other ingredient usually used in the cosmetic and / or dermatological field, in particular for the manufacture of sunscreen compositions in the form of emulsions.

 The fatty substances can consist of an oil or a wax or their mixtures. By oil is meant a compound which is liquid at room temperature. The term “wax” is intended to mean a compound which is solid or substantially solid at room temperature, and the melting point of which is generally greater than 35 C.

 As oils, mention may be made of mineral oils (petrolatum); vegetable (sweet almond oil, macadamia oil, blackcurrant seed, jojoba); synthetics such as perhydrosqualene, alcohols, fatty acids or esters (such as the benzoate of C12-CI5 alcohols sold under the name "Finsolv TN" by the company Finetex, octyl palmitate, isopropyl lanolate, triglycerides including those of capric / caprylic acids), ethoxylated or propoxylated fatty esters and ethers; (cyclomethicone, preferably with 4 or 5 silicon atoms, polydimethylsiloxane) or fluorinated, polyalkylenes.

 As waxy compounds, there may be mentioned paraffin, carnauba wax, beeswax, hydrogenated castor oil.

 Among the organic solvents, mention may be made of lower alcohols and polyols.

 The thickeners can be chosen in particular from crosslinked polyacrylic acids, guar gums and modified or unmodified celluloses such as hydroxypropylated guar gum, methylhydroxyethylcellulose, hydroxypropylmethylcellulose and silicone gums such as, for example, a polydimethylsiloxane derivative .

 The cosmetic and / or dermatological compositions according to the invention can be prepared according to techniques well known to those skilled in the art, in particular those intended for the preparation of emulsions of oil-in-water or water- type. in-oil.

 This cosmetic and / or dermatological composition can be pre-

<Desc / Clms Page number 18>

 smell in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / O or W / O / W) such as a cream, a milk, or in the form of a gel or a cream gel, powder, solid stick and optionally be packaged as an aerosol and be in the form of a foam or spray.

 Preferably, the cosmetic and / or dermatological compositions according to the invention are in the form of an oil-in-water emulsion.

 When it is an emulsion, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 e FR 2 416 008).

 The cosmetic and / or dermatological composition according to the invention is used as a protective composition for the skin or keratin materials, against ultraviolet rays, as a sunscreen composition or as a make-up product.

 When the cosmetic composition according to the invention is used for protecting the hair, it can be in the form of a shampoo, lotion, gel, emulsion, nonionic vesicular dispersion, and can constitute, for example, a composition to rinse, to apply before or after shampoo, before or after coloring or bleaching, before, during or after permanent or straightening, a styling or treating lotion or gel, a lotion or gel for brushing or setting, composition for perming or straightening, coloring or bleaching the hair.

 As an indication, for the sunscreen formulations in accordance with the invention which have an oil-in-water emulsion type support, the aqueous phase (comprising in particular hydrophilic filters) generally represents from 50 to 95% by weight, preferably from 70 to 90% by weight, relative to the entire formulation, the oily phase (comprising in particular lipophilic filters), from 5 to 50% by weight, preferably from 10 to 30% by weight, relative to the entire formulation, and the (co) emulsifier (s) from 0.5 to 20% by weight, preferably from 2 to 10% by weight, relative to the whole of the formulation.

 The example is given by way of illustration of the present invention and is in no way intended to be limiting.

<Desc / Clms Page number 19>

Example
A material according to the invention is prepared from: Tetra-n-propyl zirconate 9.36 g Absolute ethanol 2.83 g Polydimethylsiloxane-diol (PDMS-diol) 6.24 g Parsol 1789 0.08 g Water 0, 02 g tetra-n-propyl zirconate from the company Fluka, Parsol 1789 (4-tert-butyl-4'-methoxydibenzoylmethane) being sold by the company HOFFMANN-LAROCHE, and PDMS-diol having a molar mass in weight 550 (ABCR, reference DMS-S12).

 PDMS-diol is diluted in ethanol. The tetra-n-propyl zirconate is then added and the mixture is stirred for 5 minutes. The Parsol 1789 is then added with stirring. The new material is ready for use.

Application and evaluation
The new material is deposited on a glass plate (microscope slide). A film is formed on the plate after evaporation of the volatile components of the mixture. The film drying time is fast, that is to say between 1 and 3 minutes.

 The absorption band of the new material is evaluated by UV-vis absorption spectrometry. The value of #max moved to 378 nm compared to the #max of 358 nm of PARSOL 1789 before the preparation of the material. The value of the extinction coefficient (#) of the new material is at least equal to the # of the original filter. This new material is film-forming, completely remanent with water and ethanol, and does not release under these conditions and in polar and non-polar cosmetic oils.

Claims (40)

1. Material capable of being obtained by sol-gel route comprising: (a) at least one zirconium alkoxide, (b) at least one organic UV-A solar filter having a maximum absorption wavelength less than 370 nm, (c) at least one functionalized organic polymer or a precursor of such a polymer, or at least one functionalized silicone polymer or a precursor of such a polymer, (d) at least one solvent, and (e) an amount sufficient water for the partial and / or total hydrolysis of zirconium alkoxide and its condensation, said material having a maximum absorption wavelength (#max) which is in the range from 370 to 400 nm.  2. Material according to claim 1, characterized in that the zirconium alkoxide is chosen from the group consisting of: (1) alkyl zirconates corresponding to one of the following formulas: Zr (OR1) 4 (la) R-Zr (OR1) 3 (Ib) (R1O) 3Zr-R "-Zr (OR1) 3 (le) R-Zr (OR1) 2 (Id) R 'in which: RI represents a linear or branched alkyl group, in CI-30' preferably in CI-6, R and R ', independently of each other, represent a linear or branched alkyl group, a group cycloalkyl, a substituted or unsubstituted aryl group, said groups R and R ′ being able to be substituted by groups capable of reacting with the organic or silicone polymer and being able to comprise in addition a cosmetically or dermatologically active group, R "represents a linear alkylene group or branched, a cycloalkylene group, a substituted or unsubstituted arylene group, said group R "possibly being substituted by groups capable of reacting with the organic polymer. <Desc / Clms Page number 21> R 'in which: X represents a monodentate ligand comprising a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom, which can be covalently linked to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer (c), and which may contain a cosmetically or dermatologically active group, x represents the number of ligands X, R, R ', R "and RI have the same meanings as those given for formulas (la) to ( Id) above; and (3) chelated alkyl zirconates corresponding to the following formula: Zr (ORI) 4-bx '(X') x '(III) in which: RI has the same meaning as for formulas (la) to (Id) above, b represents the number of bonding atoms of the chelating group X ', x' represents the number of chelating groups X ', X' represents a chelating group comprising a nitrogen atom, a phosphorus atom, a sulfur atom and / or an oxygen atom, which can be bonded p ar covalent to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer (c), and which may comprise a cosmetically or dermatologically active group. R-Zr (OR1) 2-x (X) x (IId) Zr (OR1) 4-x (X) x (IIa) R-Zr (OR1) 3-x (X) x (IIb) (X) x (OR1) 3-x Zr-R "-Zr (ORI) 3 -x (X) x (Ile)  that or silicone and which may additionally comprise a cosmetically or dermatologically active group; (2) alkyl zirconate complexes corresponding to one of the following formulas:  3. Material according to claim 2, characterized in that said group capable of reacting with the functionalized organic polymer or the functionalized silicone polymer (c), carried by the group R, R ′ or R ″ and / or by the ligand X or X ′ can be chosen from ethylenically unsaturated groups, halogenated, hydroxylated, carboxylated groups, thiols, epoxy, esters, phosphonic groups, phosphates, phosphonates, ureido, <Desc / Clms Page number 22>  urethanes, amines, amides, amino acids and polypeptides, the acetic acid group, acetoacetate (ACAC), ethylacetoacetate, or a group deriving from EDTA and its derivatives.  4. Material according to claim 2 or 3, characterized in that the monodentate ligand X is chosen from carboxylic acids and ketones.  5. Material according to any one of claims 2 to 4, characterized in that the chelating group X 'is chosen from (3-diketones, p-ketoesters, p-ketoamines, [alpha] - and p- hydroxy acids, optionally p-hydroxylated amino acids, salicylic acid and its derivatives.  6. Material according to any one of the preceding claims, characterized in that the zirconium alkoxide is chosen from tetra-n-propyl zirconate and tetra-isopropyl zirconate.  7. Material according to any one of the preceding claims, characterized in that the zirconium alkoxide is present in an amount ranging from 0.1% by weight to 99% by weight, preferably from 0.5% to 80% by weight relative to the total weight of the material.  8. Material according to any one of the preceding claims, characterized in that the organic UV-A solar filter is chosen from: - dibenzoylmethane derivatives, - camphor derivatives, - benzimidazole derivatives, - benzoxazole derivatives , - benzophenone derivatives, - silane or polyorganosiloxane derivatives with phenone group (s), - anthranilates, and - mixtures thereof.  9. Material according to any one of the preceding claims, characterized in that the organic UV-A solar filter is chosen from: - 2-methyldibenzoylmethane, - 4-methyldibenzoylmethane, - 4-isopropyldibenzoylmethane, <Desc / Clms Page number 23>  - 4-tert-butyldibenzoylmethane, - 2,4-dimethyldibenzoylmethane, - 2,5-dimethyldibenzoylmethane, - 4,4'-diisopropyldibenzoylmethane, - 4,4'-dimethoxydibenzoylmethane, - 4-tert-butyl- 4'-methoxydibenzoylmethane, - 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, - 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, - 2,4-dimethyl-4'-methoxydibenzoylmethane, - 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.  10. Material according to any one of the preceding claims, characterized in that the organic UV-A solar filter is 4-tertbutyl-4'-methoxydibenzoylmethane.  11. Material according to any one of the preceding claims, characterized in that the organic UV-A solar filter is present in an amount ranging from 0.1% by weight to 30% by weight, preferably from 0.1% to 20% by weight relative to the total weight of the material.  12. Material according to any one of the preceding claims, characterized in that the functionalized organic or silicone polymer is a random, block and / or grafted homopolymer or copolymer chosen from: (a) homopolymers and copolymers of alkyloxazoline; (b) homopolymers and copolymers of (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene-sulfonic acid, acrylamido-2-methylpropane-sulfonic acid, methacrylate 2-sulfoethyl, vinylsulfonic acid and / or vinylphosphonic acid; (c) homopolymers of acrylic or methacrylic esters or amides, and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, sty - rene, substituted styrenes, fluoro- and perfluoro-olefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; <Desc / Clms Page number 24>  (d) homopolymers and eopolymers of vinyl alcohol; (e) homopolymers of vinyl and / or allylic esters or amides and / or methallylics, and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulphonic acids, phosphonic acids, vinyl esters and ethers , olefins, styrene, substituted styrenes, fluoro- and perfluoro-olefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; (f) polyethers; (g) polyesters; (h) homopolymers and copolymers of olefins or of cycloolefins; (i) polyamides and polyesteramides; (j) polyurethanes and polyureas which may contain polyether, polyester and / or polyorganosiloxane blocks; (k) fluoropolymers; (1) natural polymers and modified natural polymers; (m) polyorganosiloxanes; (n) polyorganophosphazenes; (o) polysilanes, polycarbosilanes or polysilazanes; (p) mixtures of these polymers.  13. Material according to any one of the preceding claims, characterized in that the functionalized organic or silicone polymer is chosen from poly (2-ethyl-2-oxazoline), vinyl acetate terpolymer, of 4 -tert-vinyl butylbenzoate and crotonic acid (65/25/10), polydimethylsiloxane-diols, polyethylene glycols, poly (amyl alcohol) and poly (vinyl pyrrolidone).  14. Material according to claim 13, characterized in that the functionalized organic or silicone polymer is a polydimethylsiloxane-diol.  15. Material according to any one of the preceding claims, characterized in that the functionalized organic or silicone polymer is present in an amount ranging from 0.1% by weight to 99% by weight, preferably from 0.5% to 80 % by weight relative to the total weight of the material.  16. Material according to any one of the preceding claims. <Desc / Clms Page number 25>  tions, characterized in that the solvent is an alcohol.  17. Material according to claim 16, characterized in that the alcohol is a lower, linear or branched alcohol.  18. Material according to claim 17, characterized in that the alcohol is ethanol.  19. Method for shifting the maximum absorption wavelength (#max) of an organic UV-A solar filter having a #max less than 370 nm, in the range from 370 to 400 nm, characterized in that that it comprises the association of this filter with a sol comprising at least one functionalized organic polymer or a precursor of such a polymer, or at least one functionalized silicone polymer or a precursor of such a polymer, at least one alkoxide of zirconium, at least one solvent, and an amount of water sufficient for the partial and / or total hydrolysis of zirconium alkoxide and its condensation.  20. The method of claim 19, characterized in that the zirconium alkoxide is chosen from the group consisting of: (1) the alkyl zirconates corresponding to one of the following formulas: Zr (ORl) 4 (the ) R-Zr (OR1) 3 (Ib) (RIO) 3Zr-R "-Zr (ORI) 3 (le) R-Zr (ORI) 2 (Id) R 'in which: R1 represents a linear or branched alkyl group, in CI-30, preferably in CI-6, R and R', independently of each other, represent a linear or branched alkyl group, a group cycloalkyl, a substituted or unsubstituted aryl group, said groups R and R ′ being able to be substituted by groups capable of reacting with the organic or silicone polymer and being able to comprise in addition a cosmetically or dermatologically active group, R "represents a linear alkylene group or branched, a cycloalkylene group, a substituted or unsubstituted arylene group, said group R ″ being able to be substituted by groups capable of reacting with the organic or silicone polymer and being able to comprise in addition a cosmetics group <Desc / Clms Page number 26> Zr (OR1) 4-bx '(X') x '(III) in which: RI has the same meaning as for the formulas (la) to (Id) above, b represents the number of bonding atoms in the group chelating X ', x' represents the number of chelating groups X ', X' represents a chelating group comprising a nitrogen atom, a phosphorus atom, a sulfur atom and / or an oxygen atom, which can be linked by covalent to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer (c), and which may comprise a cosmetically or dermatologically active group. R 'in which: X represents a monodentate ligand comprising a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom, which can be covalently linked to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer (c), and which may contain a cosmetically or dermatologically active group, x represents the number of ligands X, R, R ', R "and RI have the same meanings as those given for formulas (la) to ( Id) above; and (3) chelated alkyl zirconates corresponding to the following formula: R-Zr (OR1) 2-x (X) x (IId) R-Zr (OR1) 3-x (X) x (IIb) (X) x (ORI) 3-x Zr-R "-Zr (OR1) 3-x (X) x (Ile) Zr (OR1) 4-x (X) x (IIa)  or dermatologically active; (2) alkyl zirconate complexes corresponding to one of the following formulas:  21. Method according to claim 20, characterized in that said group capable of reacting with the functionalized organic polymer or the functionalized silicone polymer (c), carried by the group R, R ′ or R ″ and / or by the ligand X or X ′ can be chosen from ethylenically unsaturated groups, halogenated, hydroxylated, carboxylated groups, thiols, epoxy, esters, phosphonic groups, phosphates, phosphonates, ureido, urethanes, amines, amides, amino acids and polypeptides, the acid group <Desc / Clms Page number 27>  acetic, acetoacetate (ACAC), ethylacetoacetate, or a group derived from EDTA and its derivatives.  22. The method of claim 20 or 21, characterized in that the monodentate ligand X is chosen from carboxylic acids and ketones.  23. Method according to any one of claims 20 to 22, characterized in that the chelating group X ′ is chosen from ss-diketones, P-ketoesters, P-ketoamines, a- and P-hydroxy acids, optionally P-hydroxylated amino acids, salicylic acid and its derivatives.  24. Method according to any one of claims 19 to 23, characterized in that the zirconium alkoxide is chosen from tetra-n-propyl zirconate and tetra-isopropyl zirconate.  25. Method according to any one of claims 19 to 24, characterized in that the organic UV-A solar filter is chosen from: - dibenzoylmethane derivatives, - camphor derivatives, - benzimidazole derivatives, - derivatives benzoxazole, - benzophenone derivatives, - silane or polyorganosiloxane derivatives with benzophenone group (s), - anthranilates, and - mixtures thereof.  26. Method according to any one of claims 19 to 25, characterized in that the organic UV-A solar filter is chosen from: - 2-methyldibenzoylmethane, - 4-methyldibenzoylmethane, - 4-isopropyldibenzoylmethane, - 4-tert-butyldibenzoylmethane, - 2,4-dimethyldibenzoylmethane, - 2,5-dimethyldibenzoylmethane, - 4,4'-diisopropyldibenzoylmethane, - 4,4'-dimethoxydibenzoylmethane, - 4-tert-butyl-4 ' -methoxydibenzoylmethane, <Desc / Clms Page number 28>  - 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, - 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, - 2,4-dimethyl-4'-methoxydibenzoylmethane, - 2,6 -dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.  27. Method according to any one of claims 19 to 26, characterized in that the organic UV-A solar filter is 4-tert-butyl-4'-methoxydibenzoylmethane.  28. Method according to any one of claims 19 to 27, characterized in that the functionalized organic or silicone polymer is a random, block and / or grafted homopolymer or copolymer chosen from: (a) homopolymers and copolymers of alkyloxazoline; (b) homopolymers and copolymers of (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene-sulfonic acid, acrylamido-2-methylpropane-sulfonic acid, methacrylate 2-sulfoethyl, vinylsulfonic acid and / or vinylphosphonic acid; (c) homopolymers of acrylic or methacrylic esters or amides, and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, sty - rene, substituted styrenes, fluoro- and perfluoro-olefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; (d) homopolymers and copolymers of vinyl alcohol; (e) homopolymers of vinyl and / or allylic esters or amides and / or methallylics, and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulphonic acids, phosphonic acids, vinyl esters and ethers , olefins, styrene, substituted styrenes, fluoro- and perfluoro-olefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; (f) polyethers; <Desc / Clms Page number 29>  (g) polyesters; (h) homopolymers and copolymers of olefins or of cycloolefins; (i) polyamides and polyesteramides; (j) polyurethanes and polyureas which may contain polyether, polyester and / or polyorganosiloxane blocks; (k) fluoropolymers; (1) natural polymers and modified natural polymers; (m) polyorganosiloxanes; (n) polyorganophosphazenes; (o) polysilanes, polycarbosilanes or polysilazanes; (p) mixtures of these polymers.  29. Method according to any one of claims 19 to 28, characterized in that the functionalized organic or silicone polymer is chosen from poly (2-ethyl-2-oxazoline), a vinyl acetate terpolymer, of 4-tert - vinyl butylbenzoate and crotonic acid (65/25/10), polydimethylsiloxane-diols, polyethylene glycols, poly (amyl alcohol) and poly (vinyl pyrrolidone).  30. The method of claim 29, characterized in that the functionalized organic or silicone polymer is a polydimethylsiloxane-diol.  31. Method according to any one of claims 19 to 30, characterized in that the solvent is a branched or linear lower alcohol.  32. Method according to claim 31, characterized in that the alcohol is ethanol.  33. Method according to any one of claims 19 to 32, characterized in that the zirconium alkoxide is mixed with a solution of functionalized organic or silicone polymer before the addition of the filter.  34. Cosmetic and / or dermatological composition, characterized in that it comprises, in a cosmetically and / or dermatologically acceptable carrier, an effective amount of the material according to any one of claims 1 to 18.  35. Cosmetic and / or dermatological composition according to claim 34, characterized in that the material is in the form of particles obtained by drying and grinding. <Desc / Clms Page number 30>  36. Cosmetic and / or dermatological composition according to claim 34 or 35, characterized in that the effective amount of the material according to any one of claims 1 to 18 is in the range from 1% by weight to 99% by weight relative to the total weight of the cosmetic and / or dermatological composition.  37. Cosmetic and / or dermatological composition according to any one of claims 34 to 36, characterized in that the effective quantity of the material according to any one of claims 1 to 18, lies in the range preferably ranging from 5 at 60% by weight relative to the total weight of the cosmetic and / or dermatological composition.  38. Cosmetic and / or dermatological composition according to any one of claims 34 to 37, characterized in that the average size of the particles obtained by drying and grinding the material according to any one of claims 1 to 18, is within 1 '' range from 0.1 m to 20 m.  39. Cosmetic and / or dermatological composition according to claim 38, characterized in that the average size of the particles obtained by drying and grinding the material according to any one of claims 1 to 18, is in the range from 0, 1 m to 10 m.  40. Cosmetic and / or dermatological composition according to any one of claims 34 to 39, characterized in that one can additionally add an additive chosen from sun filters other than organic UV-A sun filters, tanning agents and / or artificial browning of the skin, pigments, fatty substances, organic solvents, thickeners, softeners, antioxidants.